JP7035867B2 - A vinyl chloride resin composition and a molded product formed from the composition. - Google Patents

Description

The present invention relates to a vinyl chloride resin composition and a molded product formed from the composition.

Chlorine-containing resins such as polyvinyl chloride resins are used for various purposes after being processed and molded by adding various additives such as stabilizers, lubricants, plasticizers, colorants and modifiers. Has been done. The chlorine-containing resin has problems in transparency, releasability, and heat resistance, and the chlorine-containing resin may be decomposed by heat during processing and use. In the chlorine-containing resin composition, a liquid stabilizer is used in order to improve these problems (Patent Document 1). Of these issues, mold releasability has a large effect on product productivity and tends to be emphasized. Usually, by increasing the amount of the liquid stabilizer added, the mold releasability from the mold is improved. However, when the amount of the liquid stabilizer added is increased, there is a problem that the transparency of the obtained resin composition is lowered. Therefore, there is a problem that only an amount of liquid stabilizer that can secure transparency can be used in the resin composition used for films and sheets that require transparency. There is a demand for a composition that can be suitably used for films and sheets that require transparency and that has improved mold releasability.

Japanese Unexamined Patent Publication No. 2-274748

The present invention has been made to solve the above problems, and a main object thereof is to provide a vinyl chloride resin composition having excellent transparency and releasability.

The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a liquid stabilizer for vinyl chloride resin, and polyethylene oxide having an acid value of 5 mgKOH / g or more and a density of 0.95 g / cm ³ or more. Including with wax. This vinyl chloride resin composition contains 0.001 part by weight or more of the polyethylene oxide wax with respect to 100 parts by weight of the vinyl chloride resin.
In one embodiment, the vinyl chloride resin composition contains 3 parts by weight or less of the polyethylene oxide wax.
In one embodiment, the liquid stabilizer comprises at least one selected from the group consisting of organic acid zinc salts and organic acid alkaline earth metal salts.
In one embodiment, the vinyl chloride resin composition contains 0.5 part by weight to 3 parts by weight of the liquid stabilizer with respect to 100 parts by weight of the vinyl chloride resin.
In another aspect of the invention, a molded body is provided. The molded product of the present invention is formed from the above-mentioned vinyl chloride resin composition.
In one embodiment, the molded product is a film or sheet.
In one embodiment, the molded product is for food packaging.

According to the present invention, it is possible to provide a vinyl chloride resin composition having excellent transparency and releasability. The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a liquid stabilizer for vinyl chloride resin, and polyethylene oxide having an acid value of 5 mgKOH / g or more and a density of 0.95 g / cm ³ or more. Includes wax (hereinafter also referred to as high-density polyethylene oxide wax). By using a small amount of high-density polyethylene oxide wax in combination with the liquid stabilizer, the releasability of the vinyl chloride resin composition can be significantly improved without increasing the amount of the liquid stabilizer added. Furthermore, the vinyl chloride resin composition of the present invention can also improve transparency. Therefore, it is possible to provide a vinyl chloride resin composition having both excellent transparency and releasability, which has been difficult until now.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

A. Vinyl Chloride Resin Composition The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a liquid stabilizer for vinyl chloride resin, an acid value of 5 mgKOH / g or more, and a density of 0.95 g / cm. Includes ³ or more polyethylene oxide waxes. By using the high-density polyethylene oxide wax together with the liquid stabilizer, the releasability of the vinyl chloride resin composition can be significantly improved. Further, the transparency of the vinyl chloride resin composition can be improved.

B. Vinyl chloride-based resin Examples of the vinyl chloride-based resin include pentachlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, and vinyl chloride-styrene. Polymers, vinyl chloride-isobutylene copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-styrene-maleic anhydride ternary copolymers, vinyl chloride-alkyl, cycloalkyl or arylmaleimide copolymers, vinyl chloride -Styline-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride -Acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-urethane copolymer and the like can be mentioned. These may be used alone or in combination of two or more.

The degree of polymerization of the vinyl chloride resin is preferably 700 to 2000. When the degree of polymerization of the vinyl chloride resin is within such a range, a film and a sheet having excellent moldability into a film and a sheet and having an excellent balance between strength and a feeling of touch can be obtained.

C. Liquid Stabilizer for Vinyl Chloride Resin Any suitable liquid stabilizer can be used as the liquid stabilizer for vinyl chloride resin. As the liquid stabilizer, a liquid stabilizer containing a zinc salt and / or an alkaline earth metal salt is preferably used. Since these stabilizers are stabilizers that are liquid at room temperature, have low toxicity, and have a low odor, the vinyl chloride resin composition of the present invention can be suitably used for applications such as food packaging. can. When the vinyl chloride resin composition of the present invention is used for food packaging (for example, a food packaging sheet or a food packaging stretch film), it is preferable that the organic tin stabilizer is not contained. This is because the use of an organotin-based stabilizer can cause odor to be a problem.

C-1. Zinc salt and alkaline earth metal salt As the zinc salt and alkaline earth metal salt, any suitable salt can be used. As the zinc salt and the alkaline earth metal salt, for example, an organic acid zinc salt and an organic acid alkaline earth metal salt can be used.

The zinc organic acid salt is typically obtained by reacting an organic acid with zinc oxide. In one embodiment, the zinc organic acid salt is a positive organic acid salt obtained by reacting 2 equivalents of organic acid with 1 equivalent of zinc oxide.

The organic acid is typically a carboxylic acid. Examples of the carboxylic acid include saturated fatty acids having 2 to 22 carbon atoms, unsaturated fatty acids and carbocyclic carboxylic acids. Specific examples of these include acetic acid, propionic acid, valeric acid, caproic acid, octyl acid, 2-ethylhexic acid, tridecanoic acid, isodecanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, Isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, lysynolic acid, erucic acid, behenic acid, thioglycolic acid, mercaptopropionic acid, lauryl mercaptopropionic acid, benzoic acid, para-t-butylbenzoic acid, 3- Methyl benzoic acid, dimethyl benzoic acid, amino benzoic acid, salicyl acid, aminoacetic acid, glutamic acid, oxalic acid, glutaric acid, succinic acid, malonic acid, adipic acid, phthalic acid, fumaric acid, maleic acid, malic acid, citric acid, tartrate acid. , Thiodipropionic acid, trimellitic acid, pyromellitic acid, merit acid and the like. Preferred are oleic acid, octylic acid, benzoic acid, para-t-butylbenzoic acid, 3-methylbenzoic acid, 2-ethylhexic acid, neodecanoic acid, maleic acid, trimellitic acid, and more preferably oleic acid. Octylic acid, 2-ethylhexic acid, benzoic acid, para-t-butylbenzoic acid, 3-methylbenzoic acid. As the organic acid zinc salt, only one kind may be contained in the liquid stabilizer, or two or more kinds may be contained.

The content of the zinc organic acid salt in the liquid stabilizer is preferably 5% by weight to 40% by weight, more preferably 5% by weight to 20% by weight, based on the total amount of the liquid stabilizer. When the content of the zinc organic acid salt is in such a range, there is an advantage that the coloration during the production and / or processing of the molded product is small.

The alkaline earth metal salt of an organic acid is typically obtained by reacting an organic acid with an alkaline earth metal-containing substance. Examples of the alkaline earth metal include calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba). Calcium and barium are preferred. Examples of the alkaline earth metal-containing substance include calcium hydroxide, barium hydroxide, and magnesium oxide. The organic acids are as described above. Preferred organic acids are oleic acid, benzoic acid and para-t-butylbenzoic acid. As the alkaline earth metal salt of the organic acid, only one kind may be contained in the liquid stabilizer, or two or more kinds may be contained.

The content of the alkaline earth metal salt of the organic acid in the liquid stabilizer is preferably 5% by weight to 70% by weight, more preferably 5% by weight to 50% by weight, based on the total amount of the liquid stabilizer. When the content of the alkaline earth metal salt is in such a range, there is an advantage that seizure during the production of the molded product is reduced and the long-running property is improved.

C-2. Other Ingredients The liquid stabilizer may further contain any other suitable ingredient. Examples thereof include phosphite ester compounds, plasticizers, antioxidants, epoxidized soybean oils, ultraviolet absorbers, organic solvents and the like.

D. Polyethylene Oxidized Wax The vinyl chloride resin composition of the present invention contains polyethylene oxide wax (high-density polyethylene oxide wax) having an acid value of 5 mgKOH / g or more and a density of 0.95 g / cm ³ or more. By using a high-density polyethylene oxide wax in combination with a liquid stabilizer for a vinyl chloride resin, the transparency and releasability of the vinyl chloride resin composition can be improved.

As described above, the polyethylene oxide wax used in the present invention is a high-density polyethylene oxide wax. The density of the polyethylene oxide wax is 0.95 g / cm ³ or more, preferably 0.96 g / cm ³ or more. The density of the polyethylene oxide wax is preferably 1.1 g / cm ³ or less, and more preferably 1.0 g / cm ³ or less. When the density of the polyethylene oxide wax is in such a range, the mold releasability of the obtained resin composition can be improved. If the density is less than 0.95 g / cm ³ , the effect of mold releasability may not be sufficiently obtained. In addition, coloring of the resin composition and deterioration of transparency may occur. In this specification, the density is a value measured according to ASTM D-1505.

The acid value of the polyethylene oxide wax is 5 mgKOH / g or more, preferably 7 mgKOH / g or more, and more preferably 10 mgKOH / g or more. When the acid value is in such a range, the compatibility with the resin component is improved, and the transparency of the obtained resin composition is also improved. The acid value is preferably 50 mgKOH / g or less, and more preferably 30 mgKOH / g or less. In this specification, the acid value is a value measured according to ASTM D-1386.

The polyethylene oxide wax has a viscosity at 150 ° C. of preferably 2000 cps to 85000 cps, and more preferably 3000 cps to 10000 cps. When the viscosity is in such a range, various raw materials contained in the resin composition and the polyethylene oxide wax can be uniformly mixed. In this specification, the viscosity is a value measured by a Brookfield viscometer.

A commercially available product may be used as the polyethylene oxide wax. Specifically, AC307,307A (acid value 7 mgKOH / g, density 0.98 g / cm ³ ), AC316,316A (acid value 16 mgKOH / g,) which are high-density oxidized polyethylene homopolymers manufactured by Honeywell Co., Ltd., Density 0.98 g / cm ³ ), AC325 (acid value 25 mgKOH / g, density 0.99 g / cm ³ ), AC392 (acid value 30 mgKOH / g, density 0.99 g / cm ³ ), AC330 (Acid value 30 mgKOH / g, density 0.99 g / cm ³ ), AC395, 395A (acid value 41 mgKOH / g, density 1.00 g / cm ³ ) and the like can be mentioned.

The content of the polyethylene oxide wax in the vinyl chloride resin composition is 0.001 part by weight or more, preferably 0.01 part by weight or more, and more preferably 0.05 part by weight with respect to 100 parts by weight of the vinyl chloride resin. It is more than a part. When the content of the polyethylene oxide wax is in the above range, the transparency and releasability of the vinyl chloride resin composition can be improved. The upper limit of the content of the polyethylene oxide wax is not particularly limited, but is preferably 3 parts by weight or less from the viewpoint of cost.

E. Plasticizer As the plasticizer, any suitable compound can be used. For example, terephthalic acid ester, phthalate ester, adipate ester, trimellitic acid ester and the like can be mentioned. The plasticizer may be used alone or in combination of two or more. When the liquid stabilizer contains a plasticizer, the same plasticizer may be used, or different plasticizers may be used.

When the vinyl chloride resin composition is used for processing into films and sheets, the content of the plasticizer in the vinyl chloride resin composition is preferably 10 parts by weight or more with respect to 100 parts by weight of the vinyl chloride resin. It is more preferably 20 parts by weight or more, and further preferably 30 parts by weight or more. The content of the plasticizer is, for example, 80 parts by weight or less.

F. Other Additives The vinyl chloride resin composition of the present invention may further contain any suitable additive other than the liquid stabilizer for vinyl chloride resin and the high density polyethylene oxide wax. Specific examples of additives include β-diketone compounds or metal salts thereof, epoxy compounds, fillers, pigments, dyes, cross-linking agents (or enhancers), antistatic agents, antiplate-out agents, surface treatment agents, lubricants, and the like. Examples thereof include flame retardant agents, fluorescent agents, antifungal agents, bactericides, antibacterial agents, metal deactivating agents, mold release agents, processing aids, antioxidants, light stabilizers, foaming agents and the like. The number, type, combination, blending amount and the like of the additives can be appropriately set according to the purpose. When the vinyl chloride resin composition is used in the food packaging field, it is preferable to use one that conforms to the "voluntary standards for food hygiene such as vinyl chloride resin products" of the PVC Food Sanitation Council. Details of these additives are described, for example, in Japanese Patent No. 6179740. The description of the publication is incorporated herein by reference.

G. Method for Producing Vinyl Chloride Resin Composition The vinyl chloride resin composition of the present invention is produced by any suitable method. For example, a vinyl chloride resin composition can be produced by simultaneously adding and mixing a liquid stabilizer, a high-density polyethylene oxide wax, and any other suitable additive to a vinyl chloride resin. Further, a liquid stabilizer, a high-density polyethylene oxide wax, and any other suitable additive may be sequentially added and mixed with the vinyl chloride resin to produce the product. When manufactured by sequential addition, the liquid stabilizer, high density polyethylene oxide wax, and other additives may be added in any suitable order.

H. Molded PVC The vinyl chloride resin composition can be used for any suitable application. The vinyl chloride resin composition of the present invention has excellent mold releasability. Therefore, it can be suitably used for a molded product manufactured by using a mold or the like.

The vinyl chloride resin composition may be, for example, a film, a sheet, a packaging container (for example, a tray), an electric wire covering material, an automobile interior / exterior material, an agricultural material (for example, a vinyl house), a hose, a pipe, a wall material, or a floor. Can be used for materials, hoses, leather, toys, rubber gloves, rubber boots. The vinyl chloride resin composition of the present invention is preferably used for a film or a sheet, and more preferably can be used for a food packaging sheet or a food packaging stretch film. The vinyl chloride resin composition is excellent in transparency and releasability. Therefore, it is possible to prevent plate-out during long-run processing and improve productivity. Further, since it is excellent in transparency, it can be suitably used for a food packaging sheet or a stretch film for food packaging.

When the vinyl chloride resin composition is used for food packaging applications (for example, food packaging sheets or stretch films for food packaging), the liquid stabilizer in the composition is a hyperbasic carboxylic from the viewpoint of safety. It preferably does not contain either acid salts or hyperbasic alkaline earth metal complexes. However, it may be included as an unavoidable by-product.

As a method for molding the vinyl chloride resin composition, any appropriate molding method can be adopted depending on the intended use of the molded product, a desired shape and the like. Specific examples include extrusion, ejection, calendar, inflation, and dipping. Extrusion or calendar is preferred as the film and sheet molding method. As described above, since the vinyl chloride resin composition of the present invention has excellent mold releasability, it is possible to prevent the resin composition from adhering to the mold even when it is used for extrusion molding.

When the vinyl chloride resin composition is used for food packaging applications (for example, food packaging sheets or food packaging stretch films), the molded product is preferably transparent. More specifically, the haze value of the molded product is preferably 15 or less, more preferably 10 or less. The haze value is obtained by the method described in Examples described later.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

(Preparation of liquid stabilizer)
Zinc oleate (manufactured by Sakai Chemical Industry Co., Ltd.) 8 parts by weight, zinc 2-ethylhexylate (manufactured by Kyodo Yakuhin Co., Ltd.) 4 parts by weight, calcium benzoate (manufactured by Sakai Chemical Industry Co., Ltd.) 8 parts by weight and trilauryl acid ester (manufactured by Sakai Chemical Industry Co., Ltd.) 30 parts by weight of Johoku Chemical Industry Co., Ltd.) was mixed, and 50 parts by weight of terephthalic acid ester (manufactured by J-Plus Co., Ltd.) was further added and mixed as a plasticizer and solvent to prepare a liquid stabilizer.

[Example 1]
Polyvinyl chloride resin (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: TK-1300) 100 parts by weight, terephthalic acid ester (manufactured by J-Plus Co., Ltd., trade name: DOTP) 30 parts by weight, epoxidized soybean oil (Sakai Chemical Co., Ltd.) Industrial Co., Ltd., trade name: Inbraflex A-6) 5 parts by weight, 1.5 parts by weight of the above liquid stabilizer, and wax 1 (high-density polyethylene oxide wax, manufactured by Honeywell Co., Ltd., trade name: AC-316A, Density: 0.98 g / cm ³ , acid value: 16 mgKOH / g) 0.01 part by weight was added and mixed to prepare a vinyl chloride resin composition.

[Example 2]
A vinyl chloride resin composition was obtained in the same manner as in Example 1 except that the amount of wax 1 added was 0.05 parts by weight.

[Example 3]
A vinyl chloride resin composition was obtained in the same manner as in Example 1 except that the amount of wax 1 added was 0.1 parts by weight.

[Example 4]
A vinyl chloride resin composition was obtained in the same manner as in Example 1 except that the amount of wax 1 added was 0.3 parts by weight.

(Comparative Example 1)
A vinyl chloride resin composition was obtained in the same manner as in Example 1 except that wax 1 was not added.

(Comparative Example 2)
Same as Example 4 except that wax 2 (polyethylene oxide wax, manufactured by Honeywell, trade name: AC629A, density: 0.93 g / cm ³ , acid value: 15 mgKOH / g) was used instead of wax 1. A vinyl chloride resin composition was obtained.

(Comparative Example 3)
In the same manner as in Example 4 except that wax 3 (polyethylene oxide wax, manufactured by Honeywell, trade name: AC6A, density: 0.92 g / cm ³ , acid value: 15 mgKOH / g) was used instead of wax 1. A vinyl chloride resin composition was obtained.

(Comparative Example 4)
Example 4 except that wax 4 (polyethylene homopolymer wax, manufactured by Honeywell, trade name: AC820A, density: 0.97 g / cm ³ , acid value: 0.1 mgKOH / g) was used instead of wax 1. Similarly, a vinyl chloride resin composition was obtained.

<Evaluation>
The following evaluations were carried out using the vinyl chloride resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4. The results are shown in Table 1.

1. 1. The weight of the mold releasable vinyl chloride resin was 3 kg, and the vinyl chloride resin compositions of each Example and Comparative Example were prepared.
More specifically, each material was put into a Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd., product name: FM type Henschel mixer), mixed with wings rotated at 2000 rpm, and when the temperature of the mixture reached 120 ° C. It was discharged from the Henschel mixer. The discharged mixture was kneaded using a lab plast mill (manufactured by TOYOSEIKI) for 10 minutes under the conditions of a temperature of 190 ° C., a rotation speed of 40 rpm, and a filling amount of 62 g. After kneading, the mold was disassembled and the releasability of the kneaded product was evaluated according to the following criteria.
1: Resin sticks to the mold and is difficult to remove 2: Resin sticks to the mold but can be easily removed 3: Resin sticks to the mold slightly but can be easily removed 4: There is no sticking to the mold and it can be easily removed.

2. 2. Press Transparency The vinyl chloride resin compositions obtained in each Example and Comparative Example were subjected to an 8-inch roll machine (manufactured by KANSAI ROLL) in which the roll surface temperature was adjusted to 175 ° C. and the roll gap was 0.3 mm to 0.5 mm. The mixture was kneaded for 5 minutes to prepare a roll sheet having a thickness of 0.3 mm. 20 sheets of the obtained sheets were stacked and held at 100 kg / cm ² for 10 minutes using a press machine (manufactured by TOYOSEIKI, product name: MINI TEST PRESS-10) in which the surface temperature was set to 160 ° C. Then, a test piece was prepared. Next, the haze value (turbidity) of the obtained test piece was measured with a spectrocolorimeter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name: SQ-2000) and used as an index of transparency.

All of the vinyl chloride resin compositions obtained in Examples 1 to 4 had excellent mold releasability. Furthermore, the haze value was low, and both excellent releasability and transparency were achieved. On the other hand, in the vinyl chloride resin compositions obtained in Comparative Examples 1 to 4, the resin adhered to the mold, and it was difficult to remove the resin from the mold. There was also room for improvement in transparency.

The vinyl chloride resin composition of the present invention can be used for molded products such as films and sheets. In particular, it can be suitably used as a film for food packaging.

Claims (6)

With vinyl chloride resin,
A liquid stabilizer for vinyl chloride resin containing at least one selected from the group consisting of an organic acid zinc salt and an organic acid alkaline earth metal salt ,
A vinyl chloride resin composition containing polyethylene oxide wax having an acid value of 5 mgKOH / g or more and a density of 0.96 g / cm ³ or more.
The polyethylene oxide wax is contained in an amount of 0.001 part by weight or more based on 100 parts by weight of the vinyl chloride resin.
A vinyl chloride resin composition that does not contain an organotin stabilizer . The vinyl chloride resin composition according to claim 1, which contains 3 parts by weight or less of the polyethylene oxide wax. The vinyl chloride resin composition according to claim 1 or 2 , wherein the liquid stabilizer is contained in an amount of 0.5 part by weight to 3 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. A molded product formed from the vinyl chloride resin composition according to any one of claims 1 to 3 . The molded product according to claim 4 , which is a film or a sheet. The molded product according to claim 5 , which is for food packaging.